1-(naphthyl and naphthyloxy-acetyl-2,2-dialkyl hydrazine acids and their use as herbicides

ABSTRACT

The 1-(naphthyl and naphthyloxy)-acetyl-2,2-dialkyl hydrazine acids have been found to be active pre-emergent herbicides. These compounds are especially active against Canadian thistle and field bindweed.

United States Patent 1191 Alt 1 Dec. 16, 1975 l-(NAPHTHYL AND 521,8072/1956 Canada .1 71/118 IIYDRAZINE ACIDS AND THEIR USE AS HERBICIDESBuu-Ho1 et a1., Mechanism of Action of Tuberculostatic Hydrazides,(1952), CA 47, p. 2358 (1953). [75] Inventor: Gerhard II. Alt, CreveCoeur, Mo. Weinswig et a1 Monoamine Oxidase Inhibitors [73] Assignee:Monsanto Company, St. Louis, M0. 610," CA 63, P- 13171 Liberman et 211.,New Isopropylhydrazide Mono- [22] 1973 amine etc, (1961), CA 56, pp.114l61 1417 [21] Appl. No: 375,397 (1962).

Related Appficmion Data Buu-Hoi et a1 11, Tubercuiostatic I-Iydrazidesand [62] Division ofSer. No.214,382 Dec. 30, 1971,1 m. N0. Th'ckeners(1953) CA 7580'7581 3,767,621 Kraus et a1., Growth-regulating Substancesas Herbicides, (1947), CA 41, p. 3902, (1947). [52] U.S. C1 71/118;71/76 Brian, Synthesis of ders. of N,N-dimethy1hydrazine [51] Int. Cl.AOIN 9/20 etc,. (1971), J. Med. Chem. (1971), pp. 1133-1134. [58] Fieldof Search 71/118 Primary ExaminerG1ennon H. Hollrah [56] ReferencesCited Attorney, Agent, or FirmWi11iam T. Black UNITED STATES PATENTS2,341,868 2/1944 Hitchcock et a1. 1. 71/118 [57] ABSTRACT 2,472,3476/1949 Sexton 71/118 3,439,018 4/1969 Brookes et a1.... 71/118 ThelimaphFhyl and i 3,481,730 12/1969 Douros, Jr. et a1... 7l/ll8 hydralmeq been found to be aetlve P 3,71s,4ss 2/1973 Baker 71/118 emergentherbleldee These eempelmds are espeelally active against Canadianthistle and field bindweed.

6 Claims, No Drawings l-(NAPHTHYL AND NAPHTHYLOXY-ACETYL-2,2-DIALKYLHYDRAZINE ACIDS AND THEIR USE AS HERBICIDES This is a division ofapplication Ser. No. 214,382, filed Dec. 30, 1971, now US. Pat. No.3,767,623.

This invention relates to novel l-( 2-substituted)acetyl-2,2-dialkylhydrazines. More particularly, this invention relates to the Z-naphthyland 2-naphthyloxy substituted acetyl dialkyl hydrazines. These newcompounds have been found to be useful as pre-emergent herbicides.

In accordance with this invention, it has been discovered that novelhydrazines of the formula wherein R is a naphthyl group, R and R areeach lower alkyl groups containing from 1 to 6 carbon atoms and n is aninteger of or I; possess herbicidal activity.

A preferred embodiment of this invention are those compounds of theabove formula in which R and R are alkyl groups having a maximum of 3carbon atoms.

The naphthyl groups represented by R include both the l-substitutednaphthyl group and the 2-substituted naphthyl groups, that is a andB-naphthyl groups. Illustrative of the alkyl groups represented by R andR are, for example, methyl, ethyl, propyl, isopropyl, butyl, secondarybutyl, tertiary butyl, pentyl, hexyl and its isomers.

In general, the compounds of this invention are prepared by the reactionof 1,1-dialkyl hydrazine with the appropriate acid chloride in a benzenesolution. In general, acid chloride is added slowly, with stirring, andcooling by means of an ice bath to a solution of the hydrazine in anorganic solvent which is non-reactive towards either the hydrazine orthe acid chloride. The reaction mixture is then allowed to warm to roomtemperature with continuous stirring and water added to precipitate thesolid product. The solid product can be recrystallized in an organicsolvent medium such as ethyl acetate-petroleum ether mixtures to yield apure product.

The temperature at which the reaction is conducted is not narrowlycritical and can range from as low as to 30C or even higher, dependingupon the solvent employed and the speed of addition of the reactants.

For convenience, one can employ two moles of the hydrazine for each moleof the acid chloride, the molar excess of hydrazine being employed toaccept the liberated hydrogen chloride. Equimolar amounts of thereactants can be employed if an acid acceptor such as pyradine,triethylamine or sodium carbonate is employed.

Among the organic solvents which can be employed in producing thecompounds of this invention are the aprotic solvents such as benzene andthe like which are non-reactive towards the dimethyl hydrazine or theacid chloride.

The starting naphthoxy or naphthyl substituted acetic acid halides arecommercially available or are prepared by-methods well known in the art.

2 The following examples serve to further illustrate this invention. Allparts are by weight unless otherwise expressly set forth.

EXAMPLE 1 To a solution of 1,1-dimethyl hydrazine (0.3 mols) in benzenemilliliters) was added dropwise with stirring and cooling in an icebath, a solution of 2-(2-naphthyloxy)-acetyl chloride (0.15 mols) inbenzene (9O mls.). The reaction mixture was allowed to come to roomtemperature and stirred for 18 hours. Approximately 300 mls. of waterwas added to the reaction mixture and the solid material whichprecipitated out was removed by filtration. The material wasrecrystallized from ethyl acetate-petroleum ether mixture and had amelting point of 107 to 109C. This solid material was identified asl-(2-naphthyloxyacetyl)-2,2- dimethyl hydrazine and gave the followinganalysis:

Calcd: C, 68.83; H, 6.6; N, 11.47. Found: C, 68.73; H, 6.67; N, 11.35.

EXAMPLE 2 The procedure of Example 1 was followed, however, 2-(1-naphthyl)-acetyl chloride was substituted for the acid chlorideemployed in Example 1 to give I-( lnaphthylacetyl)-2,2-dimethylhydrazine having a melting point of 137 to 139C. The compound gave thefollowing analysis:

Calcd: C, 73.66; H, 7.06; N, 12.27. Found: C, 73.70; H, 7.18; N, 12.14.

Following the procedure of Examples 1 and 2, the following compounds canbe prepared:

l-( Z-naphthyloxyacetyl )-2,2-diethyl hydrazine 1-( 2-naphthyloxyacetyl)-2,2-dipropyl hydrazine l 2-naphthyloxyacetyl )-2,2-dibutyl hydrazinel-( 2-naphthyloxyacetyl )-2,2-dihexyl hydrazine l-(1-naphthyloxyacetyl)-2,2.-dimethyl hydrazine l-(l-naphthyloxyacetyl)-2,2.-diethyl hydrazine l-(1-naphthyloxyacetyl)-2,2-dipentyl hydrazine 1-( l-naphthylacetyl )-2,2-diethyl hydrazine l-( 1-naphthylacetyl)-2,2-dipropyl hydrazine l-(1-naphthylacetyl)-2,2-dibutyl hydrazine 1-(l-naphthylacetyl)-2,2-dihexyl hydrazine l-( 2-naphthylacetyl)-2,2-dimethyl hydrazine l-(2-naphthylacetyl)-2,2-diethyl hydrazinel-(Z-naphthylacetyl)-2,2dibutyl hydrazinel-(Z-naphthylacetyl)-2,2-dihexyl hydrazine The compounds of the presentinvention possess herbicidal activity. This herbicidal activity isillustrated by the following examples.

EXAMPLE 3 This example illustrates pre-emergent activity of thecompounds of this invention.

A good grade of top soil is placed in aluminum pans and compacted to adepth of We to /2 inch from the top of each pan. A pre-determined numberof seeds and vegetative propagules of each. of several plant species areplaced on top of the soil in the pans. The seeds and propagules arecovered with a measured amount of soil containing the chemical admixedthroughout. The herbicidal composition is applied at a rate of 5 poundsper acre by spraying the soil to be used as a cover layer, thenthoroughly mixing the soil and herbicidal compound. The pans are placedon the sand of a greenhouse bench and watered as needed. The soil in thepans absorbs moisture through the apertured bottom of the pans. Theplants are observed at the end of approxi- 3 4 mately 14 days and theresults recorded.

The 'pre-emergent herbicidal activity of the com- Numerical Herbicida]pounds of this invention is measured by the average Scale Activitypercent control of each of the plant species. The aver- No phytotoxicityage percent control is converted to a relative numerical 5 1 Slight P 'Xscale for the sake of brevity and simplicity in the exami ple. Thepre-emergent herbicidal activity index used in 4 Plants dead the Tableis defined as follows:

Average Percent Numerical The results of the post-emergent tests aregiven in Control Scale Table III.

0 25 0 TABLE III 26 so 1 51 75 2 Compound of Examples 76 100 3 PlantSpecie 1 Canada Thistle 2 I Nutsedge 0 O The pre-emergent herbicidalactivity of some of the Quackgrass 0 O v df th d d h Johnson Grass 0 0compoun s o e present invention is recor e in t e Cocklebu, 1 followingTable. Velvet Leaf 0 2 Morning Glory 1 3 TABLE I Lambsquarter 1 3Smartweed 1 Compound of Examples Downy Brome 1 O Plant Specie 2 1Barnyard Grass 0 O Canada Thistle 3 3 Nutsedge l 0 Quackgtass 3 0 Forthe sake of brevity and simplicity, the term ac- Johnson Grass 2 OCocklebu, 0 3 tive ingredient is used in this specification to describeVelvet Leaf 3 2 the naphthyl and naphthyloxy acetyl hydrazmes of thisMorning Glory 3 3 invention I Lambsquarter 3 3 Smanweed The termherbicide as used herein and in the ap- B'Ome 0 pended claims meansmaterials which control the Barnyard Grass l 0 growth of plants either(1) all plants in a given locus or (2) selectively control the growth ofone or more plant In a second test at the same rate and following the iq n l presence.of other plants In hke manger r 5 herbicidal is used toidentify the overall and selective above procedure but employingdifferent plant species, i-

control activity of the compositions of this invention. the pre-emergentresults are shown in Table I1.

The term plant as used herein and in the appended TABLE 11 claims isinclusive of dormant seeds, germinant seeds, Compound of Examplesgerminative seeds, emerging seedlings and established Plant Specie 2 140 woody and herbaceous vegetation including the roots Soybean 3 3 andabove-ground portions. Sugar Beet 3 2 The term control as used hereinand in the apf O ended claims is inclusive of the actions of l) killinRice 3 l p g Sorghum 2 0 (2) inhibiting growth, reproduction orproliferation, g q g g z h g g and (3) removing, destroying or otherwisediminishing g 'gg 3 2 the occurrence and activity of plants and isapplicable Hemp Sesbania 2 1 to any of the stated actions, or anycombination Lambsquarter 3 3 thereof I Smartweed' 2 2 velvet L f 2 3 Theterm herbicidal formulation or composition as w y Brome 1 g used hereinmeans a naphthyl or naphthyloxy acetyl 522322 I hydrazine of thisinvention in combination with an Crabgrass 2 1 ad uvant to be definedhereinbelow. i

The active ingredients hereindefined are suitable for both pre-emergentand post-emergent plant, applica- 55 tion. That is, they are effectivein controlling the EXAMPLE 4 growth of germinant seeds, emergingseedlings and In a post-emergent herbicidal test, the activemgredrestablished vegetation by exposing the seeds, emerging ents ineach case is applied in spray form to 21 day old seedlings, or the rootsor above-ground portions to the specimens of the plants (speciesindicated hereinafter). action of an effective amount of one or more ofthese The herbicidal sprays are acetone-water solutions conherbicidallyactive compounds; however, the best retaining surface active agent andvarying amounts of the sults are usually obtained in a pre-emergentapplicaactive ingredient. The solution are applied to the plants tion.Such constitutes a preferred embodiment of the in different pans atrates equal to 4 pounds of active method of controlling plants.ingredient per acre. The treated plants are placed in a In foliartreatment for the modification of vegetative greenhouse and the effectsare observed and recorded after approximately 14 days.

The post-emergent herbicidal activity index used in this example isdefined as follows:

growth, the active ingredients are applied in amounts from about 0.1 toabout 50 or more pounds per acre, preferably about 0.1 to 15 pounds peracre in foliar treatments. In soil applications, it is desirable thatthe combination with a material referred to in the art as an' adjuvantin liquid or solid form. The usual purpose of adjuvants are tofacilitate application of the herbicidal composition and at the desireddosage rate. Herbicidal formulations are prepared by admixing the activeingredient with one or more adjuvants which includes diluents,extenders, carriers and conditioning agents to provide compositions inthe form of finely-divided particulate solids, granules, pellets,solutions, dispersions or emulsions. Thus, the active ingredient can beused with an adjuvant such as a finely-divided particulate solid, aliquid of organic origin, water, a wetting agent, dispersing agent, anemulsifying agent or any suitable combination of these.

Suitable adjuvants of the foregoing types are not here defined in detailas to composition, particle size, relative amounts, etc., since they arewell known in the art.

In general, the active ingredients may be formulated with the activeingredient in minor or major proportions in accordance with the tablebelow:

Concentration of Type of Formulation Active Ingredient l. Granules ofrelatively large particle size to 50% 2. Powdery dusts 2 to 90% 3.Wettable powders 2 to 90% 4. Emulsifiable concentrates 5 to 95% 5.Solutions .01 to 95% 6. One of the less common types of formulationsdepending on the desired mode of application .01 to 95% In addition toadjuvants the compounds of this inven tion can be used in combinationwith fertilizers and/or other pesticides such as insecticides,fungicides, nematocides, and/or other phytotoxicants, and the like.

Having now described the invention, many ramifications and modifiedembodiments will readily occur to those skilled in the art. Insofar assuch variations do not depart from the spirit and scope of the inventiondescribed in this application, they are intended to be embraced by theappended claims in their broadest construction. What is claimed is:

1. Herbicidal composition comprising an inert carrier and a herbicidallyeffective amount of a compound of the formula wherein R is a naphthylgroup, R and R are each independently an alkyl group of from 1 to 6carbon atoms and n is O or 1.

2. Composition of claim 1 wherein the compound is l-(1-naphthylacetyl)-2,2-dimethyl hydrazine.

3. Composition of claim 1 wherein the compound is 1-( 2-naphthyloxyacetyl)-2,2-dimethyl hydrazine.

4. A herbicidal method which comprises applying to plants or the plantlocus a herbicidally effective amount of a compound of the formulawherein R is a naphthyl group, R and R are each independently an alkylgroup of from 1 to 6 carbon atoms and n is 0 or 1.

5. A method of claim 4 wherein the compound is 1-( l-naphthylacetyl)-2,2-dimethyl hydrazine.

6. A method of claim 4 wherein the compound is l-( Z-naphthyloxyacetyl)-2,2-dimethyl hydrazine.

1. HERBICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND A HERBICIDALLYEFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. Composition of claim 1wherein the compound is 1-(1-naphthylacetyl)-2,2-dimethyl hydrazine. 3.Composition of claim 1 wherein the compound is 1-(2-naphthyloxyacetyl)-2,2-dimethyl hydrazine.
 4. A herbicidal method which comprisesapplying to plants or the plant locus a herbicidally effective amount ofa compound of the formula
 5. A method of claim 4 wherein the compound is1-(1-naphthylacetyl)-2,2-dimethyl hydrazine.
 6. A method of claim 4wherein the compound is 1-(2-naphthyloxy acetyl)-2,2-dimethyl hydrazine.